Chain growth reaction process

ABSTRACT

A process is disclosed for the preparation of zinc alkyl chain growth products via a catalyzed chain growth reaction of an alpha-olefin on a zinc alkyl, wherein the chain growth catalyst system employs a group 3-10 transition metal, or a group 3 main group metal, or a lanthanide or actinide complex, and optionally a suitable activator. The products can be further converted into alpha-olefins by olefin displacement of the grown alkyls as alpha-olefins from the zinc alkyl chain growth product, or into primary alcohols, by oxidation of the resulting zinc alkyl chain growth product to form alkoxide compounds, followed by hydrolysis of the alkoxides.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a Continuation-in-Part of application Ser. No.11/476,206 filed Jun. 28, 2006, now U.S. Pat. No. 7,767,771, which is acontinuation of application Ser. No. 09/921,695 filed Aug. 6, 2001, nowU.S. Pat. No. 7,087,686, the entire contents of each of which are herebyincorporated by reference.

CHAIN GROWTH REACTION PROCESS

This invention relates to the preparation of zinc alkyls by the chaingrowth reaction of a lower olefin, especially ethylene, with a lowermolecular weight zinc alkyl and more specifically to a chain growthprocess on zinc, catalysed by a catalyst system comprising a group 3-10transition metal, group 3 main group metal, lanthanide or actinidecomplex, and optionally a suitable activator.

The reactivity of zinc alkyls (and zinc alkenyls) with lower olefins hasbeen reported, see Journal of Organometallic Chemistry 1973, 60, p 1-10;Liebigs Ann. Chem. 1975, p 1162-75; Journal of Organometallic Chemistry1981, 221, p 123-130. Di-tert-butyl zinc reacts with 2 equivalents ofethylene between −20 C and 75 C to give bis(3,3-dimethylbutyl)zinc, eachzinc alkyl group effectively inserting only one ethylene molecule.Dialk-2-enylzinc compounds add to 2 equivalents of ethylene to give thedialk-4-enylzinc compounds, each zinc alkenyl group reacting with onlyone ethylene molecule. A second type of reaction between an alkyl zincspecies and an olefin also is known. It involves an (α-haloalkyl)zincintermediate reacting with an olefin to produce a cyclopropane productand is frequently referred to as the Simmons-Smith procedure [see J. Am.Chem Soc. 81, 4256 (1959); Ibid, 86, 1337, (1964); Org React., 20, 1-131(1973).]

There have been no reports of the preparation of zinc alkyls by reactionof a lower olefin with lower molecular weight zinc alkyl, where morethan one olefin inserts into an alkylzinc bond or where the chain growthprocess is catalysed by a catalyst system. These types of reactionswould be examples of stoichiometric chain growth, the catalysed versionis known in the field as catalysed chain growth. (See eq. 1, M=Zn)

$\begin{matrix}{{R - {ML}_{n} + {p\; C_{2}H_{4}}}\overset{Catalyst}{\rightarrow}{{R\left( {C\; H_{2}C\; H_{2}} \right)}_{p} - {{ML}_{n}.}}} & {{Eq}.\mspace{14mu} 1}\end{matrix}$

Catalysed chain growth of ethylene has been demonstrated for aluminiumalkyls (M=Al in eq. 1), where an activated metallocene compound acts asthe catalyst system. This is described in U.S. Pat. Nos. 5,210,338 and5,276,220. According to the process described in U.S. Pat. No.5,210,338, a catalyst system comprising metallocene halo-complexes ofzirconium and hafnium and related complexes in combination withmethylaluminoxane (MAO) produce aluminium alkyls, where the ethylenechain growth products are best described by the Schulz-Flory statisticaldistribution; polyethylene is a persistent co-product. The Schulz-Florydistribution is described by the formula χ_(p)=β/(1+β)^(p), where χ_(p)is the mole fraction containing p added ethylenes and β is theSchulz-Flory distribution coefficient. According to the processdescribed in U.S. Pat. No. 5,276,220, aluminum alkyl chain growth iscatalysed at mild temperatures and pressures with a catalyst systemcomprising an activated actinide metallocene compound. In addition, theethylene chain growth products from the process described in U.S. Pat.No. 5,276,220 provides a Poisson-like alkyl chain length distributionand avoids formation of a polymeric co-product. A Poisson chain lengthstatistical distribution is described by the formula χ_(p)=(x^(p)e^(−x))/p!, where χ_(p) is the mole fraction with p added ethylenes andx is the Poisson distribution coefficient equal to the average number ofethylenes added per Al—C bond. As described in these patents, thecatalysed ethylene chain growth processes with aluminium alkyls operateat dramatically lower pressures and temperatures than does thenon-catalysed, stoichiometric ethylene chain growth on aluminium alkyls(100-200° C., 2000-4000 psi ethylene).

A number of ethylene chain growth processes on aluminium alkyls havebeen found to be particularly useful in the production of linearalpha-olefins and linear alcohols. Alpha-olefins can be generated fromalkyl chain growth on aluminium, by displacement of the olefin productwith ethylene either simultaneous with the chain growth reaction toyield a Schulz-Flory-like distribution of products or in a second,separate step. It is found that the catalysed chain growth process givesmore highly linear alkyl groups than those produced under the moreforcing conditions required to effect the uncatalysed chain growthreaction.

However, in certain instances, the physical and chemical characteristicsof the aluminium alkyl species present in the processes described abovelimit the usefulness of the known catalysed chain growth processes.Aluminium alkyl compounds form compositionally complex monomeric anddimeric species that can be difficult to separate from one another orfrom the product olefins. They can react with product olefins to makeunwanted by-products and they are highly reactive, even with relativelyunreactive chemicals such as carbon dioxide, and may, over time,inactivate the metallocene chain growth catalyst systems, therebygreatly increasing their cost.

It is therefore desirable to develop catalysed chain growth processesthat do not possess the limitations of the known processes usingaluminium alkyls, or for which the limitations are substantiallylessened.

We have discovered that some of the above problems can be successfullyaddressed by using zinc alkyl compounds instead of aluminium alkyls. Inaccordance with the present invention therefore, there is provided aprocess for the preparation of zinc alkyl chain growth products via acatalysed chain growth reaction of an alpha-olefin on a zinc alkyl,comprising contacting the zinc alkyl with a chain growth catalyst systemwhich employs a group 3-10 transition metal, or a group 3 main groupmetal, or a lanthanide or actinide complex, and optionally a suitableactivator. This zinc alkyl chain growth product may be a single materialor a mixture of compounds, and may be used to prepare alpha olefins,alcohols, lubricants, speciality chemicals, and pharmaceuticals,catalyst systems, polymeric intermediates, or polymeric materials.

Also provided is a process for the preparation of alpha-olefins by thecatalysed chain growth reaction of an alpha-olefin on a zinc alkyl,followed by olefin displacement of the grown alkyls as alpha-olefinsfrom the zinc alkyl chain growth product, where the chain growthcatalyst system employs a group 3-10 transition metal, group 3 maingroup metal, lanthanide or actinide complex, and optionally a suitableactivator.

Also provided is a process for the preparation of primary alcohols bythe chain growth reaction of alpha-olefin on a zinc alkyl, oxidation ofthe resulting zinc alkyl chain growth product to form alkoxidecompounds, followed by hydrolysis of the alkoxides to produce primaryalcohols, where the chain growth catalyst system employs a group 3-10transition metal, group 3 main group metal, lanthanide or actinidecomplex, and optionally a suitable activator.

The invention also provides in another aspect compositions of alkyl zinccomplexes where the alkyl groups follow a substantially Poisson-likestatistical distribution of chain lengths up to about 200 carbon atoms,and compositions of alkyl zinc complexes where the alkyl groups follow asubstantially Schulz-Flory-like statistical distribution of chainlengths up to about 50,000 carbon atoms.

Examples of olefins suitable for chain growth include, but are notlimited to, C₂ to C₂₆ alpha-olefins, and mixtures thereof, with C₂ toC₁₆ linear alpha-olefins being the preferred olefins. For thepreparation of highly linear zinc alkyl chain growth product, andmaterials derived therefrom such as linear alpha olefins and linearprimary alcohols, ethylene is the most preferred olefin. Depending uponthe intended use, it may be desirable to produce, via the presentinvention, a Schulz-Flory-like distribution of grown alkyl species,while in other instances a Poisson-like distribution of grown zinc alkylspecies may be advantageous. Other product distributions anddistributions intermediate between those characterized by Schulz-Floryand Poisson statistics can be achieved by those skilled in the art bymanipulating the catalyst and/or the process conditions. The skeletalarchitecture of the chain grown alkyls and their derivatives similarlycan be varied by skillful control of the catalyst(s), olefin feedstocks,initial alkylzinc species, and the reaction conditions. For example, toproduce a polymeric intermediate containing a low temperature,ethylene-based elastomer or plastomer structure, one could employ asuitable bis(imine)nickel or Pd catalyst such as[1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethylbutadiene]nickel(II)bromide together with ethylene with or without an additional comonomer,and an alkyl zinc species, the resulting Zn-capped material being usefulfor making AB-type block copolymers.

The catalysed chain growth reaction can be performed under a range ofprocess conditions that are readily apparent to those skilled in theart: as a homogeneous liquid phase reaction in the presence or absenceof an inert hydrocarbon diluent such as toluene or heptanes; as atwo-phase liquid/liquid reaction; as a slurry process where the catalystand/or the reaction products have little or no solubility or aresupported; as a bulk process in which essentially neat zinc alkyls orolefins serve as the dominant medium; as a gas-phase process in whichvolatile zinc alkyl species and olefins contact the catalyst from agaseous state. In certain instances, the chain growth reaction can becarried out in the presence of the products of subsequent reactions ofthe chain grown zinc alkyls, a non-limiting example being tetradeceneand other chain grown linear alpha olefins constituting part or all ofthe diluent utilized in liquid phase (catalysed) addition of ethylene todibutylzinc. The catalysed chain growth reactions may be performed inthe known types of gas-phase reactors (such as vertically orhorizontally stirred-bed, fixed-bed, or fluidised-bed reactors,)liquid-phase reactors (such as plug-flow, continuously stirred tank, orloop reactors,) or combinations thereof.

Reaction temperatures for the catalysed chain growth reactions may varyfrom sub-ambient temperatures (below 20° C.) to approximately 200° C.Pressures of ethylene may be varied from about 1 psig to about 5000psig, although it is generally advantageous to operate at pressuresbelow 1500 psig.

Suitable zinc alkyl feed compounds for the chain growth are any speciesor mixture of species containing the R′R″CH—Zn— or R′R″C—Zn— moieties,where R′ and R″ are independent and can be hydrogen, hydrocarbyl, silyl,or substituted hydrocarbyl group; R′ and R″ may be connected and thusform a cyclic species; in the case of R′R″C—Zn—, the C bonded to the Znis unsaturated [non-limiting examples of R′R″C—Zn— compounds beingdi-phenyl-Zn and (C₅H₅)ZnEt]. Compounds containing the R′R″CH—Zn— moietyinclude dialkyl zincs and alkyl zinc hydrides, which can be representedby the formula R_(m)ZnH_(n) where m is 1 or 2 and n is 0 or 1, m+n=2,and each R is independently C₁ to C₃₀ alkyl. Mixtures of these compoundscan be used. Specific non-limiting examples of suitable feed compoundsinclude dimethylzinc, diethylzinc, di-n-butylzinc, di-n-hexylzinc,dibenzylzinc, di-n-decylzinc, di-n-dodecylzinc, and the like. Preferredzinc alkyl feedstocks for the chain growth process are low molecularweight zinc alkyls having alkyl groups with even carbon numbers andespecially diethylzinc and di-n-butylzinc. Diethylzinc is commerciallyavailable while routes for preparing other dialkylzinc are well known inthe literature and include thermal disproportionation of alkyl zinchalides, alkylation of zinc salts by alkyl aluminium compounds, andmetal exchange of Zn with dialkylmercury compounds.

The chain growth catalyst system employs a group 3-10 transition metal,group 3 main group metal, lanthanide or actinide complex, and optionallya suitable activator.

Suitable complexes are the metallocenes, which may contain at least onecyclopentadienyl-based ring ligands. For the purposes of this patentspecification the term “metallocene” is defined as containing one ormore unsubstituted or substituted cyclopentadienyl or cyclopentadienylmoiety in combination with a group 3-6 transition metal, a group 3 maingroup metal, a lanthanide or an actinide. In one embodiment themetallocene catalyst component is represented by the general formula(C_(p))_(m)MR_(n)R′_(p) wherein at least one C_(p) is an unsubstitutedor, preferably, a substituted cyclopentadienyl ring, a substituted orunsubstituted ring system such as an indenyl moiety, a benzindenylmoiety, a fluorenyl moiety or the like, or any other ligand capable ofη-5 bonding such as borolles or phospholes; M is a Group 4, 5 or 6transition metal, a lanthanide or an actinide; R and R′ areindependently selected halogen, hydrocarbyl group, or hydrocarboxylgroups having 1-20 carbon atoms or combinations thereof; m=1-3, n=0-3,p=0-3, and the sum of m+n+p equals the oxidation state of M, preferablym=2, n=1 and p=1. The Cp can be substituted with a combination ofsubstituents, which can be the same or different. Non limiting examplesof substituents include hydrogen or a linear, branched or cyclic alkyl,alkenyl or aryl radical having from 1 to 20 carbon atoms.

In another embodiment the metallocene catalyst component is representedby the formulas:(C₅R′_(m))_(p)R″_(s)(C₅R′_(m))MeQ_(3-p-x), orR″_(s)(C₅R′_(m))₂MeQ′

wherein Me is a Group 4, 5 or 6 transition metal, a lanthanide or anactinide; at least one C₅R′_(m) is a substituted cyclopentadienyl, eachR′, which can be the same or different is hydrogen, alkyl, alkenyl,aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms ortwo carbon atoms joined together to form a part of a substituted orunsubstituted ring or rings having 4 to 20 carbon atoms, R″ is one ormore of or a combination of a carbon, a germanium, a silicon, aphosphorous or a nitrogen atom containing radical bridging two (C₅R′_(m)) rings, or bridging one (C₅R′_(m)) ring to M, when p=0 and x=1otherwise “x” is always equal to 0, each Q which can be the same ordifferent is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicalhaving from 1 to 20 carbon atoms, halogen, or alkoxides, Q′ is analkylidene radical having from 1-20 carbon atoms, s is 0 or 1 and when sis 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1.

Preferred metallocenes are bis(pentamethylcyclopentadienyl)zirconiumdichloride, bis(pentamethylcyclopentadienyl)hafnium dichloride,bis(tetramethylcyclopentadienyl)zirconium dichloride,(pentamethylcyclopentadienyl)zirconium trichloride,(tetramethylcyclopentadienyl)(t-butylamido)(dimethylsilane)titaniumdimethyl, and (pentamethylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride.

Other suitable complexes are the group 3-10 transition metal, group 3main group metal, lanthanide or actinide complexes containing a neutral,monoanionic, dianionic ligands, which can be mondentate, bidentate,tridentate or tetradentate, and which comprise at least one N, P, O or Satom. Non-limiting examples of such complexes are described in WO96/23010, WO 97/02298, WO 98/30609, WO 99/50313, WO 98/40374, WO00/50470, WO 98/42664, WO 99/12981, WO 98/27124, WO 00/47592, WO01/58966 and our own co-pending applications PCT 02/02247 and PCT02/02144.

A preferred class of transition metal complexes are representedgenerically by the Formula (I):

wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV],Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV],Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II],Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III],Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], Pd[II], X representsan atom or group covalently or ionically bonded to the transition metalM; Y¹ is C or P(R^(c)); Y² is —O(R⁷), —O (in which case the bond from Oto M is covalent), —C(R^(b))═O, —C(R^(b))═N(R⁷), —P(R^(d))═N(R⁷) or—P(R^(b))(R^(d))═O; R^(a), R^(b), R^(c), R^(d), R⁵ and R⁷ are eachindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′₃where each R′ is independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substitutedheterohydrocarbyl, and any adjacent ones may be joined together to forma ring; G is either a direct bond between Y¹ and Y², or is a bridginggroup, which optionally contains a third atom linked to M when q is 1; Lis a group datively bound to M; n is from 0 to 5; m is 1 to 3 and q is 1or 2.

One preferred complex is represented by the general formula (II):

wherein R^(x) is selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl, substitutedheterohydrocarbyl or SiR′₃ where each R′ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl and substituted heterohydrocarbyl, and all othersubstituents are as defined above. In the complex of Formula (II), M ispreferably a Group IV metal, particularly Ti, Zr, a Group VI metal,particularly Cr, or a Group VIII metal, particularly Ni, Co, or Pd.Preferably R^(a) and R^(b) are joined together to form a phenyl, whichis preferably substituted. Preferred substituents are C₁-C₆ alkyl orC₆-C₂₄ aryl or aralkyl. In particular, the phenyl group may besubstituted at the position adjacent the oxygen linkage with a t-butylgroup or an anthracenyl group, which may itself be substituted.

A further preferred complex is that of Formula (III):

wherein M is Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III],Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II],Pd[II], Cu[I], Cu[II]; X represents an atom or group covalently orionically bonded to the transition metal M; R^(a) and R^(b) are eachindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl or SiR′₃where each R′ is independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substitutedheterohydrocarbyl, and R^(a) and R^(b) may be joined together to form aring; R⁵ and R⁷ are each as defined above; and L is a group dativelybound to M; n is from 0 to 5; m is 1 to 3 and q is 1 or 2. Preferably Mis Fe, Ni or Pd.

A particularly preferred complex has the following Formula (IV):

wherein M[T] is Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV],Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV],Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III],Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III],Rh[II], Rh[III], Ni[II], Pd[II]; X represents an atom or groupcovalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; Y¹ is C or P(R^(c)), A¹ to A³ are each independently Nor P or CR, with the proviso that at least one is CR; R, R^(c), R⁴ andR⁶ are each independently selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl, substitutedheterohydrocarbyl or SiR′₃ where each R′ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl and substituted heterohydrocarbyl; and R⁵ and R⁷ areeach as defined above.

Preferably Y¹ is C. Preferably A¹ to A³ are each independently CR whereeach R is as defined above. In alternative preferred embodiments, A¹ andA³ are both N and A² is CR, or one of A¹ to A³ is N and the others areindependently CR. Examples of such embodiments include the following:

wherein R¹, R² and R³ are each independently H, or C₁-C₁₀ alkyl, aryl oraralkyl. Generally in the above Formulae, R⁵ and R⁷ are preferablyindependently selected from substituted or unsubstituted alicyclic,heterocyclic or aromatic groups, for example, phenyl, 1-naphthyl,2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl,2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl,2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2-t-butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl,2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl,3,5-dichloro2,6-diethylphenyl, and 2,6-bis(2,6-dimethylphenyl)phenyl,cyclohexyl, pyrolyl, 2,5 dimethylpyrolyl and pyridinyl.

In a preferred embodiment R⁵ is represented by the group “P” and R⁷ isrepresented by the group “Q” as follows:

wherein R¹⁹ to R²⁸ are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R¹⁹ to R²⁸are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents.

Preferably at least one of R¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl. More preferably at least one of R¹⁹ and R²⁰, and atleast one of R²¹ and R²², is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl. Most preferably R¹⁹,R²⁰, R²¹ and R²² are all independently selected from hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl. R¹⁹, R₂₀, R²¹ and R²² are preferably independentlyselected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl,tert.-butyl, n-pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl,phenyl and benzy.

R¹, R², R³, R⁴, R⁶, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁵, R²⁶ and R²⁸ arepreferably independently selected from hydrogen and C₁ to C₈hydrocarbyl, for example, methyl, ethyl, n-propyl, n-butyl, t-butyl,n-hexyl, n-octyl, phenyl and benzyl.

A particularly preferred complex has the Formula Z

wherein all the substituents are as defined above. Preferred complexesare 2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl₂ and2,6-diacetylpyridinebis(2,6 diisopropyl anil)FeCl₂.

In an alternative embodiment, applicable to all the above structures, R⁵is a group having the formula —NR²⁹R³⁰ and R⁷ is a group having theformula —NR³¹R³², wherein R²⁹ to R³² are independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, and may be linked toform one or more cyclic substituents. Examples of such compounds aredisclosed in WO 00/50470.

Another preferred substituent for both R⁵ and R⁷ are pyrazolyl groups,as described in our own co-pending application PCT 02/02247.

Particularly preferred is the substituent having the formula (II):

The atom or group represented by X in the complexes disclosed above canbe, for example, selected from halide, sulphate, nitrate, thiolate,thiocarboxylate, BF₄ ⁻, PF₆ ⁻, hydride, hydrocarbyloxide, carboxylate,hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl, orβ-diketonates. Examples of such atoms or groups are chloride, bromide,methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide,ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxideand benzoate. Preferred examples of the atom or group X in the compoundsof Formula (I) are halide, for example, chloride, bromide; hydride;hydrocarbyloxide, for example, methoxide, ethoxide, isopropoxide,phenoxide; carboxylate, for example, formate, acetate, benzoate;hydrocarbyl, for example, methyl, ethyl, propyl, butyl, octyl, decyl,phenyl, benzyl; substituted hydrocarbyl; heterohydrocarbyl; tosylate;and triflate. Preferably X is selected from halide, hydride andhydrocarbyl. Chloride is particularly preferred.

L may be for example an ether such as tetrahydrofuran or diethylether,an alcohol such as ethanol or butanol, a primary, secondary or tertiaryamine, or a phosphine.

The chain growth catalyst system optionally employs a suitableactivator. The activator compound for the catalyst of the presentinvention is suitably selected from organoaluminium compounds andhydrocarbylboron compounds, and can comprise more than one of thesecompounds. Suitable organoaluminium compounds include trialkyaluminiumcompounds, for example, trimethylaluminium, triethylaluminium,tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride,diethylaluminium chloride and alumoxanes. Alumoxanes are well known inthe art as typically the oligomeric compounds which can be prepared bythe controlled addition of water to an alkylaluminium compound, forexample trimethylaluminium. Such compounds can be linear, cyclic ormixtures thereof. Commercially available alumoxanes are generallybelieved to be mixtures of linear and cyclic compounds. The cyclicalumoxanes can be represented by the formula [R¹⁶AlO]_(s) and the linearalumoxanes by the formula R¹⁷(R¹⁸AlO)_(s) wherein s is a number fromabout 2 to 50, and wherein R¹⁶, R¹⁷, and R¹⁸ represent hydrocarbylgroups, preferably C₁ to C₆ alkyl groups, for example methyl, ethyl orbutyl groups. Another suitable type of organoaluminium compound istris(pentafluorophenyl)aluminium.

Examples of suitable hydrocarbylboron compounds aredimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,H⁺(OEt₂)[(bis-3,5-trifluoromethyl)phenyl]borate,trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl)boron.

It is generally found that the quantity employed is sufficient toprovide 0.1 to 20,000 atoms, preferably 1 to 2000 atoms of aluminium orboron per transition metal atom of the transition metal complex.

The complexes utilised in the present invention can if desired comprisemore than one of the above-mentioned group 3-10 transition metal, group3 main group metal, lanthanide or actinide complexes. The catalyst maycomprise, for example a mixture of2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂ complex and2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ complex, or a mixtureof 2,6-diacetylpyridine(2,6-diisopropylanil)CoCl₂ and2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂, In addition to saidone or more defined transition metal compounds, the catalysts of thepresent invention can also include one or more other types of transitionmetal compounds or catalysts.

The complexes of the present invention can be unsupported or supportedon a support material, for example, silica, silica/alumina, magnesiumchloride, zeolites, alumina or zirconia, or on a polymer or prepolymer,for example polyethylene, polystyrene, or poly(aminostyrene), or onanother heterogeneous catalyst. In another embodiment, both thecomplexes and activators are co-supported on the support material,polymer or prepolymer.

The chain growth reaction illustrated in equation 3 may utilize a neatzinc alkyl medium or may utilize a hydrocarbon solvent diluent such astoluene or heptane. When the chain is being grown by ethylene, higher(C₃-C₂₀+ alpha-olefins such as 1-octene may be used as a solvent orco-solvent. Reaction temperatures may vary from approximately roomtemperature 20° C. to 150° C. Pressures of ethylene may be varied fromabout 15 psig to about 1500 psig.

The mole ratio of transition metal to zinc alkyl may be varied fromabout 1×10⁻⁷ to 1×10⁻¹ and preferably from about 1×10⁻⁶ to 1×10⁻², andmore preferably is in the range 2×10⁻⁶ to 5×10⁻³.

When conducting the chain growth reaction with some catalysts, it ishelpful to activate the catalyst in order to avoid an induction period.One convenient method is to incubate the catalyst in aluminoxanesolution in a separate vessel for about 5 minutes at 20° C. Subsequentaddition to the zinc alkyl permits immediate uptake of ethylene.

As demonstrated by the examples below C₂ to C₂₀+ alpha-olefins can berecovered from alkylzinc compounds by catalytic displacement with, forexample, a Ni catalyst, using ethylene and/or other alpha olefins as thedisplacing olefin. Alternatively, the chain growth products can beoxidized to zinc alkyl peroxide intermediates, oxidized and hydrolyzedusing known procedures to produce linear primary alcohols, or used inknown procedures to make other specialty materials.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects of the present invention will now be described,by way of example,

FIG. 1 is a graph showing the GPC of polyethylene produced in accordancewith the process of the invention in the presence of diethylzinc and inthe absence of diethylzinc;

FIG. 2 is a graph showing the distribution of even alkanes at differentdiethylzinc concentrations:

FIG. 3 is a graph showing yields of even alkanes at different reactiontimes;

FIGS. 4 and 5 are graphs similar to the graph of FIG. 1;

FIG. 6 is a graph showing the distribution of even alkanes;

FIG. 7 is a graph similar to the graph of FIG. 1;

FIG. 8 is a graph showing that diethylzinc does not affect the branchinglevel in the reaction;

FIG. 9 is a graph similar to the graph of FIG. 6;

FIG. 10 is a graph similar to the graph of FIG. 1;

FIG. 11 is a graph showing the hexane versus 1-hexene content of thetoluene fraction;

FIG. 12 is a graph showing the GC-analysis of the toluene solution;

FIG. 13 is a graph similar to the graph of FIG. 6;

FIG. 14 is a graph showing the GPC of toluene insoluble fractionsproduced in accordance with the process of the invention in the presenceof diethylzinc and in the absence of diethylzinc;

FIG. 15 is a graph similar to the graph of FIG. 14;

FIG. 16 is a graph showing the GPC of samples taken after 1, 2, 4, 6, 8,and 12 minutes;

FIG. 17 is a graph similar to the graph of FIG. 15; and

FIG. 18 is a graph similar to the graph of FIG. 16.

The invention is further illustrated by, but is not intended to belimited to, the following general procedures and examples.

EXAMPLES

Manipulation of complexes, zinc alkyls, and optional activators, as wellas the assembly and disassembly of reactors were conducted under anitrogen atmosphere. Ethylene was polymer grade, used withoutpurification. 2,6-bis[1-(2,6-diisopropylphenyl)imino)ethyl]pyridineiron(II) chloride and2,6-bis[1-(2,6-diisopropylphenyl)imino)ethyl]pyridine cobalt(II)chloride were prepared according to the established procedure describedin WO 99/12981.2,4-bis[(2,6-diisopropylphenylimino)benzyl]-6-methylpyrimidine iron(II)chloride was prepared according to the procedure disclosed in GB0100249. The complex used in Example 14 was prepared according to theprocedure in WO 00/50470. The complex used in Example 15 was preparedaccording to the procedure of GB 0112023.Bis[N-(3-tert-butylsalicylidene)aniline]zirconium(IV) dichloride wasprepared according to the procedure described in J. Am. Chem. Soc. 2001,123, 6847-6856. Bis[N-(3-tert-butylsalicylidene)aniline]hafnium(IV)dichloride was prepared according to the procedure described inMacromol. Rapid Commun. 2002, 23, 1118-1123.[N-(3-(9-triptycenyl)salicylidene)-(8-aminoquinoline)]chromium(III)dichloride was prepared according to the procedure described in Chem.Commun. 2002, 1038-1039.

Bis(n-butylcyclopentadienyl)zirconium dichloride and[1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethylbutadiene]nickel(II)bromide were prepared according to the established literatureprocedures. MAO (10 wt % in toluene) was obtained from Witco.Bis(cyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride, nickel(II)acetylacetonate, trimethyl aluminium (2M in toluene), dodecane(anhydrous), cyclohexane (anhydrous), and nonane (anhydrous) wereobtained from Aldrich. Undecane was obtained from Aldrich and distilledover CaH₂ prior to use. Diethyl zinc solution was obtained from Acros(0.87M in toluene) or Aldrich (1.1M in toluene or heptane).rac-Ethylenebis(indenyl)zirconium(IV) dichloride and nickel naphthenatewas obtained from Strem Chemical. 1-hexene (98.07% pure) from BP wasused.

Example A

Synthesis of dihexylzinc

n-Hexylmagnesiumchloride was prepared by addition of a solution of1-chlorohexane (13 g, 108 mmol, filtered through neutral active alumina)in 50 ml diethylether to 3.2 g Mg in 40 ml diethylether over a period of30 min. The mixture was allowed to reflux for an additional 2 h. Thesolution was transferred to 53 ml of a 1.0 M solution of ZnCl₂ (53 mmol)in diethylether over a period of 30 min and the reaction mixture wasstirred overnight. The mixture was filtered and the remaining salts werewashed twice with 100 ml diethylether. The combined filtrates wereconcentrated by removal of the solvent in vacuo. Vacuum distillation(0.08 mbar, 68° C.) gave dihexylzinc as a colourless liquid in a 63%yield (7.83 g, 33.2 mmol). ¹H NMR (250 MHz, C₆D₆, 298 K): δ 1.57 (brquintet, 2H, Zn—CH₂—CH ₂—, ³J=7 Hz), 1.36-1.28 (m, 6H, —CH ₂—CH ₂—CH₂—CH₃), 0.93 (br t, 3H, —CH₃, ³J=7 Hz), 0.29 (t, 2H, Zn—CH₂—, ³J=7 Hz)¹³C NMR (62.9 MHz, C₆D₆, 298 K): δ 36.6, 32.3, 26.7, 23.1, 16.3, 14.4.

Example 1 Catalysed Chain Growth Using an Iron pyridylbisimine Catalyst

A) Preparation of Catalyst Solution

In a Schlenk flask was placed2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine iron(II) chloride(31 mg; 0.050 mmol) and 24 ml toluene. To the colourless solution wasadded MAO (3.0 ml), giving a clear orange solution that was stirred for5 minutes at room temperature.

B) Chain Growth Reaction

In a 500 ml Schlenk flask was placed toluene (50 ml) and diethylzinc(2.5 ml of a 0.87M solution in hexane). The Schlenk flask with suba sealwas evacuated and back-filled with ethylene (0.75 bar overpressure).Into this mixture was injected 2.5 ml of the catalyst solution preparedunder A (containing 5.0 μmol Fe) giving a pale yellow solution. Thereaction was run at room temperature for 30 minutes, whereby anexothermic reaction occurred within 1 minute. After 15 minutes thereaction mixture became viscous and cloudy and the temperature dropped.The reaction was stopped after 30 minutes by hydrolysis with 50 mldilute HCl solution (2M). The precipitated polymer was filtered, washedwith acetone, dried overnight in a vacuum oven (60° C.) and analysed byGPC and ¹H-NMR. The organic fraction of the filtrate was separated,dried with MgSO₄ and filtered. The alkane content of this organicfraction was determined by gas chromatography using2,2,4,4,6,8,8-heptamethylnonane as an internal reference. The GPC-traceof the toluene-insoluble fraction (M_(N)=600, M_(W)=700, PDI=1.1,activity=1000 g/mmol·h·bar) is shown in FIG. 1 together with the GPC forpolyethylene produced under similar conditions but in the absence ofdiethylzinc (M_(N)=10000, M_(W)=192000, PDI=19.2, activity=1200g/mmol·h·bar). ¹H-NMR analysis of the product formed in the presence ofdiethylzinc shows the product to be fully saturated (43.6 methyl and 0.2vinyl end-groups per 1000 C). GC-analysis of the toluene-solublefraction confirmed the presence of even-numbered alkanes.

Example 2 The Effect of an Increase in the Diethylzinc-Concentration onCatalysed Chain Growth Using an Iron pyridylbisimine Catalyst

In experiments similar to that described in Example 1, the effect ofdiethylzinc-concentration on the catalysed chain growth was studied (1μmol Fe complex used in Example 1, 100 eq MAO, 1 bar ethylene, 50 mltoluene, 30 min, RT).

The distribution of even alkanes (determined by GC) in thetoluene-solutions produced with 2200 eq diethylzinc (activity=2800g/mmol·h·bar), 4400 eq diethylzinc (activity=3000 g/mmol·h·bar) and 8700eq diethylzinc (activity=2000 g/mmol·h·bar) are shown in FIG. 2.

Example 3 Time-Dependent Catalysed Chain Growth Using an Ironpyridylbisimine Catalyst

A) Preparation of Catalyst Solution

In a Schlenk flask was placed Fe complex used in Example 1 (12 mg; 0.020mmol) and 24 ml toluene. To the colourless solution was added MAO (1.2ml), giving a clear orange solution that was stirred for 5 minutes atroom temperature.

B) Chain Growth Reaction

In a 250 ml jacketed two-necked roundbottom flask was placed toluene (50ml), 0.40 ml distilled undecane and diethylzinc (4.0 ml of a 0.87Msolution in hexane).

The flask was equipped with suba seals, a thermometer and water coolingand was evacuated and back-filled with ethylene (0.75 bar overpressure).Into the solution was injected 2.5 ml of the catalyst solution preparedunder A (containing 2.0 μmol Fe) giving a pale yellow solution. Within30 seconds after injecting the catalyst the temperature rose from 19° C.to 32° C. where after the temperature dropped. The reaction wasmonitored by taking samples (˜2 ml) from the reaction mixture through acannula. The samples were hydrolysed with 2 ml dilute HCl solution (2M)and the alkane content of the toluene fraction was determined by GCusing undecane as an internal reference. After 8 minutes the reactionmixture became viscous and cloudy. The reaction was stopped after 20minutes by hydrolysis with 50 ml dilute HCl solution (2M). GC analysisof the samples 1-7 shows even alkanes with a Poisson distribution (Table1 below and FIG. 3).

TABLE 1 Yields (in mg) of different alkanes (C8-C34) for samples 1-7Sample C8 C10 C12 C14 C16 C18 C20 1 (2 min.) 120.2 186.4 226.1 219.5186.6 130.5 85.5 2 (4 min.) 58.7 108.0 170.0 215.2 232.1 220.1 188.7 3(6 min.) 32.9 57.4 104.3 154.0 193.9 214.8 215.5 4 (9 min.) 17.4 28.958.6 99.6 145.6 187.4 218.1 5 (12 min.) 16.6 18.5 38.5 69.7 110.1 154.7198.1 6 (15 min.) 9.8 15.3 31.8 58.8 95.5 137.4 179.3 7 (18 min.) 14.813.4 27.5 51.1 84.2 123.8 166.0 Sample C22 C24 C26 C28 C30 C32 C34 1 (2min.) 50.9 28.4 15.3 7.8 4.0 2 (4 min.) 148.8 108.3 74.4 48.7 30.7 19.111.6 3 (6 min.) 199.8 170.4 136.3 103.8 75.8 54.1 37.7 4 (9 min.) 234.4232.6 215.7 189.5 159.3 129.6 99.7 5 (12 min.) 233.7 253.8 255.2 242.4220.2 189.4 141.3 6 (15 min.) 213.7 232.9 233.2 220.1 199.0 172.6 132.67 (18 min.) 203.3 225.9 229.7 219.4 200.0 173.7 133.8

Example 4 Catalysed Chain Growth Using a zirconocene

In experiments similar to that described in example 1, the effect ofbis(pentamethylcyclopentadienyl)zirconium dichloride (ZrCp*₂Cl₂) on thechain growth reactions of diethylzinc was studied (5 μmol ZrCp*₂Cl₂, 100eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT).

The GPC-traces of the toluene-insoluble fractions produced with 440 eqdiethylzinc (M_(N)=1600, M_(W)=12000, PDI=7.7, activity=3500g/mmol·h·bar), 1750 eq diethylzinc (M_(N)=700, M_(W)=1500, PDI=2.2,activity=2600 g/mmol·h·bar) and in the absence of diethylzinc(M_(N)=9300, M_(W)=72000, PDI=7.7, activity=1200 g/mmol·h·bar) are shownin FIG. 4. ¹H-NMR analysis shows the product formed in the presence ofdiethylzinc to be fully saturated (14.9 methyl and 0.2 vinyl end-groupsper 1000 C for the reaction with 440 eq ZnEt₂ and 37.5 methyl and 0.1vinyl end-groups per 1000 C for the reaction with 1750 eq ZnEt₂).

Example 5 Catalysed Chain Growth Using a metallocene Catalyst

In experiments similar to that described in Example 1, the effect ofrac-ethylenebis(indenyl)zirconium(IV) dichloride (rac-(EBI)ZrCl₂) on thechain growth reactions of diethylzinc was studied (5 μmolrac-(EBI)ZrCl₂, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT).

The GPC-traces of the toluene-insoluble fractions produced with 440 eqdiethylzinc (M_(N)=800, M_(W)=1600, PDI=1.9, activity=2400 g/mmol·h·bar)and in the absence of diethylzinc (M_(N)=66000, M_(W)=261000, PDI=3.9,activity=1300 g/mmol·h·bar) are shown in FIG. 5. ¹H-NMR analysis showsthe product formed in the presence of diethylzinc to be fully saturated(31.9 methyl and 0.2 vinyl end-groups per 1000 C).

Example 6 Catalysed Chain Growth Using a Metallocene Catalyst

In an experiment similar to that described in example 3 samples weretaken from a reaction mixture containing (rac-(EBI)ZrCl₂) anddiethylzinc (2 μmol rac-(EBI)ZrCl₂, 100 eq MAO, 2200 eq ZnEt₂, 1 barethylene, 50 ml toluene, RT). Only the first sample taken after 2.5 minresulted in toluene-soluble alkanes with a distribution shown in FIG. 6together with the GC-trace from a comparable run with Fe1 (see example3).

Example 7 Catalysed Chain Growth Using a Ni(α-diimine) Catalyst

In experiments similar to that described in Example 1, the effect of[1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-2,3-dimethylbutadiene]nickel(II)bromide ((dab)NiBr₂) on the chain growth reactions of diethylzinc wasstudied (5 μmol (dab)NiBr₂, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 1h, RT).

The GPC-traces of the polymer produced with 440 eq diethylzinc(M_(N)=23000, M_(W)=67000, PDI=2.9, activity=250 g/mmol·h·bar), with1750 eq diethylzinc (M_(N)=4300, M_(W)=8400, PDI=1.9, activity=300g/mmol·h·bar) and in the absence of diethylzinc (M_(n)=193000,M_(w)=435000, PDI=2.3, activity=300 g/mmol·h·bar) are shown in FIG. 7.FIG. 8 shows that diethylzinc does not affect the branching level inthese reactions.

Example 8 Catalysed Chain Growth Using an Iron pyrimidylbisimineCatalyst

In experiments similar to that described in example 1, the effect of2,4-bis[(2,6-diisopropylphenylimino)benzyl]-6-methylpyrimidine iron (II)chloride (N4Fe1) on the chain growth reactions of diethylzinc wasstudied (5 μmol N4Fe1, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 30min, RT). The product consisted of toluene-soluble, even alkanes (>95%)with the distribution shown in FIG. 9.

Example 9 Catalysed Chain Growth Using a Cobalt Pyridylbisimine Catalyst

In experiments similar to that described in example 1, the effect of2,6-bis[1-((2,6-diisopropylphenyl)imino)ethyl]pyridine cobalt(II)chloride on the chain growth reactions of diethylzinc was studied (5μmol Co, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT). TheGPC-traces of the toluene-insoluble fractions produced with 500 eqdiethylzinc (M_(N)=1800, M_(W)=3500, PDI=2.0, activity=600 g/mmol·h·bar)and in the absence of diethylzinc (M_(N)=3300, M_(W)=11000, PDI=3.2) areshown in FIG. 10. ¹H-NMR and GC analysis show 85% of the product formedin the reaction with 500 eq diethylzinc to be fully saturated (11.3methyl and 1.3 vinyl end-groups per 1000 C).

Example 10 Displacement of 1-hexene from dihexylzinc

A 250 ml Schlenk flask with suba seal containing 645 mg dihexylzinc(2.74 mmol) and 40 ml toluene was evacuated and back-filled withethylene (0.75 bar overpressure). A solution of 35.4 mg Ni(acac)₂ (0.138mmol) in 3 ml toluene was injected into the solution. The reaction wasfollowed with time by taking samples, hydrolysing them with 2M HCl andcomparing the hexane versus 1-hexene content of the toluene fraction(determined by GC), as shown in FIG. 11.

Example 11 Catalysed Chain Growth Followed by Chain Displacement ofα-olefins from dialkylzinc

A mixture of dialkylzinc was produced in a reaction similar to example 1(2 μmol Fe1, 1750 eq ZnEt₂, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 8min, RT). After 8 min reaction the contents of the Schlenk flask weretransferred into another Schlenk containing dry silica. After 15 minstirring the toluene solution was filtered into a Schlenk containing asolution of Ni(acac)₂ (0.35 mmol) in 10 ml toluene under 1 bar ethylenepressure. The reaction mixture was hydrolysed after 30 min by additionof 50 ml 2M HCl. GC-analysis of the toluene solution (FIG. 12) shows adistribution consisting of 75% even 1-alkenes and 25% even alkanes.

Example 12 Displacement of ethylene from diethylzinc by 1-hexene

A heavy-walled Fischer-Porter tube containing 8.0 mL diethylzinc, 1.0 mLnonane, and 15.5 mL 1-hexene was purged with ethylene (1 bar) threetimes, sampled (t₀), heated for 1.0 h at 60° C. under 100 psi ethylene,cooled to room temperature and sampled (t=60 min). Nickel naphthenate(0.66 mL of 1.26×10⁻² M in dodecane) solution was added to the solutionin the F-P tube and allowed to stir for 1.0 h at room temperature,sampled (t=120 min), the gas volume above the solution was purged threetimes with nitrogen (1 bar), brought to 100 psi nitrogen, then heated at60° C. for 1 h, and sampled (t=180 min). The samples were hydrolysed andhexene and hexane analysed by GC. The amount of hexane corresponds tothe amount of hexyl-zinc moieties formed from the displacement ofethylene from the diethylzinc. The extent of displacement is provided inTable 2.

TABLE 2 Hexene Displacement of Et—Zn Catalysed by 43 ppm Ni Total Time(minutes) R—Zn Groups as Hexyl (%) 0 0.00 60 0.41 120 15.14 180 31.49

Example 13 Catalysed Chain Growth Using a Metallocene Catalyst

In experiments similar to that described in example 1, the effect ofbis(n-butylcyclopentadienyl)zirconium dichloride (Zr(CpBu)₂Cl₂) on thechain growth reactions of diethylzinc was studied (5 μmolrac-(EBI)ZrCl₂, 2000 eq ZnEt₂ 100 eq MAO, 1 bar ethylene, 50 ml toluene,30 min, RT). The product consisted of toluene-soluble, even alkanes(>95%) with the distribution shown in FIG. 13.

Example 14 Catalysed Chain Growth Using an Iron Pyridylbisimine Catalyst

In experiments similar to that described in example 1, the effect of theiron pyridyl bisimine complex below on the chain growth reactions ofdiethylzinc was studied (5 μmol Fe, 2000 eq ZnEt₂ 100 eq MAO, 1 barethylene, 50 ml toluene, 30 min, RT). GC-analysis of the toluene-solublefraction shows a series of oligomers of which 75% is even alkanes and25% is even alkenes.

Example 15 Catalysed Chain Growth Using an Iron Pyridylbisimine Catalyst

In experiments similar to that described in example 1, the effect of theiron pyridyl bisimine complex below on the chain growth reactions ofdiethylzinc was studied (5 μmol Fe, 2000 eq ZnEt₂ 100 eq MAO, 1 barethylene, 50 ml toluene, 30 min, RT). GC-analysis of the toluene-solublefraction shows a series of oligomers of which 70% is even alkanes and30% is even alkenes.

Example 16 Catalysed Chain Growth Using a Phenoxyimine ZircomiumCatalyst

In experiments similar to that described in example 1, the effect ofbis[N-(3-tert-butylsalicylidene)aniline]zirconium(IV) dichloride on thechain growth reactions of diethylzinc was studied (5 μmol Zr complex,100 eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT).

The GPC-trace of the toluene-insoluble fractions produced with 550 eqdiethylzinc (M_(N)=1000, M_(W)=1100, PDI=1.1, activity=1700g/mmol·h·bar) and in the absence of diethylzinc (M_(N)=5500,M_(W)=128000, PDI=23, activity=1600 g/mmol·h·bar) is shown in FIG. 14.¹H-NMR analysis shows the product formed in the presence of diethylzincto be fully saturated (33.6 methyl and 0.5 vinyl end-groups per 1000 C).

Example 17 Catalysed Chain Growth Using a Phenoxyimine Hafnium Catalyst

In experiments similar to that described in example 1, the effect ofbis[N-(3-tert-butylsalicylidene)aniline]hafnium(IV) dichloride on thechain growth reactions of diethylzinc was studied (5 μmol Hf complex,100 eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT).

The GPC-trace of the toluene-insoluble fractions produced with 550 eqdiethylzinc (M_(N)=800, M_(W)=900, PDI=1.1, activity=900 g/mmol·h·bar)and in the absence of diethylzinc (M_(N)=7000, M_(W)=65000, PDI=9.4,activity=800 g/mmol·h·bar) is shown in FIG. 15. ¹H-NMR analysis showsthe product formed in the presence of diethylzinc to be fully saturated(51.3 methyl and 0.0 vinyl end-groups per 1000 C).

Example 18 Time-Dependent Catalysed Chain Growth Using PhenoxyimineHafnium Catalyst

In experiments similar to that described in example 2A and 2B, the timedependent catalysed chain growth effect ofbis[N-(3-tert-butylsalicylidene)aniline]hafnium(IV) dichloride withdiethylzinc was studied (2 μmol Hf complex, 500 eq MAO, 2200 eq ZnEt₂, 1bar ethylene, 50 ml toluene, 30 min, RT). GC analysis of the samplestaken after 1, 2, 4, 6, 8 and 12 minutes shows even alkanes with aPoisson distribution (FIG. 16).

Example 19 Catalysed Chain Growth Using a Phenoxyimine Chromium Catalyst

In experiments similar to that described in example 1, the effect of[N-(3-(9-triptycenyl)salicylidene)-(8-aminoquinoline)]chromium(III)dichloride on the chain growth reactions of diethylzinc was studied (5μmol Cr complex, 100 eq MAO, 1 bar ethylene, 50 ml toluene, 30 min, RT).

The GPC-trace of the toluene-insoluble fractions produced with 550 eqdiethylzinc (M_(N)=500, M_(W)=600, PDI=1.2, activity=1400 g/mmol·h·bar)and in the absence of diethylzinc (M_(N)=900, M_(W)=1800, PDI=2.0,activity=1800 g/mmol·h·bar) is shown in FIG. 17. ¹H-NMR analysis showsthe product formed in the presence of diethylzinc to be mainly saturated(50.0 methyl and 7.5 vinyl end-groups per 1000 C).

Example 20 Time-Dependent Catalysed Chain Growth Using PhenoxyimineChromium Catalyst

In experiments similar to that described in example 2A and 2B, the timedependent catalysed chain growth effect of[N-(3-(9-triptycenyl)salicylidene)-(8-aminoquinoline)]chromium(III)dichloride with diethylzinc was studied (2 μmol Cr complex, 100 eq MAO,2200 eq ZnEt₂, 1 bar ethylene, 50 ml toluene, 30 min, RT). GC analysisof the samples taken after 2, 4, 6, 8 and 12 minutes shows even alkaneswith a Poisson distribution (FIG. 18).

The invention claimed is:
 1. A composition comprising: i) a plurality ofzinc alkyl compounds; and ii) one or more chain growth catalysts; atleast one of the chain growth catalysts being selected from the groupconsisting of: a) a complex of Formula (IV)

wherein M[T] is Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV],Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV],Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III],Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III],Rh[II], Rh[III], Ni[II], or Pd[II]; X represents an atom or groupcovalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; Y¹ is C or P(R^(c)), A¹ to A³ are each independently Nor P or CR, with the proviso that at least one is CR; and R, R^(c), R⁴,R⁵, R⁶ and R⁷ are each independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substitutedheterohydrocarbyl or SiR′₃ where each R′ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; b) a complex ofFormula (III)

wherein M is Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III],Ru[II], Ru[III], Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Pd[II],Cu[I], or Cu[II]; X represents an atom or group covalently or ionicallybonded to the transition metal M; R^(a) and R^(b) are each independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl, substituted heterohydrocarbyl or SiR′₃ where each R′is independently selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl, and R^(a) and R^(b) may be joined together to form aring; R⁵ and R⁷ are each as defined above; and L is a group dativelybound to M; n is from 0 to 5; m is 1 to 3 and q is 1 or 2; c) a complexof Formula (II)

wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV],Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV],Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II],Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III],Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], or Pd[II], Xrepresents an atom or group covalently or ionically bonded to thetransition metal M; R^(a), R^(b), R^(x), and R⁵ are each independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl, substituted heterohydrocarbyl or SiR′₃ where each R′is independently selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl, and any adjacent ones may be joined together to forma ring; L is a group datively bound to M; n is from 0 to 5; m is 1 to 3and q is 1 or 2; and d) a complex of Formula (I)

wherein M is Y[II], Y[III], Sc[II], Sc[III], Ti[II], Ti[III], Ti[IV],Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV],Nb[II], Nb[III], Nb[IV], Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II],Cr[III], Mn[II], Mn[III], Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III],Ru[IV], Co[II], Co[III], Rh[II], Rh[III], Ni[II], or Pd[II], Xrepresents an atom or group covalently or ionically bonded to thetransition metal M; Y¹ is C or P(R^(c)); Y² is —O(R⁷), —O (in which casethe bond from O to M is covalent), —C(R^(b))═O, —C(R^(b))═N(R⁷),—P(R^(b))(R^(d))═N(R⁷) or —P(R^(b))(R^(d))═O; R^(a), R^(b), R^(c),R^(d), R⁵ and R⁷ are each independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substitutedheterohydrocarbyl or SiR′₃ where each R′ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, and any adjacentones may be joined together to form a ring; G is either a direct bondbetween Y¹ and Y², or is a bridging group, which optionally contains athird atom linked to M when q is 1; L is a group datively bound to M; nis from 0 to 5; m is 1 to 3 and q is 1 or
 2. 2. The composition of claim1 wherein the mole ratio of transition metal M to zinc alkyl is between1×10⁻⁷ and 1×10⁻¹.
 3. The composition of claim 1 further comprising anactivator.
 4. The composition of claim 1 wherein the chain growthcatalyst system comprises a complex of the Formula (IV):

wherein M[T] is Ti[II], Ti[III], Ti[IV], Zr[II], Zr[III], Zr[IV],Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV],Nb[V], Ta[II], Ta[III], Ta[IV], Cr[II], Cr[III], Mn[II], Mn[III],Mn[IV], Fe[II], Fe[III], Ru[II], Ru[III], Ru[IV], Co[II], Co[III],Rh[II], Rh[III], Ni[II], or Pd[II]; X represents an atom or groupcovalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; Y¹ is C or P(R^(c)), A¹ to A³ are each independently Nor P or CR, with the proviso that at least one is CR; and R, R^(c), R⁴,R⁵, R⁶ and R⁷ are each independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substitutedheterohydrocarbyl or SiR′₃ where each R′ is independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl.
 5. The compositionaccording to claim 4 wherein Y¹ is C, and A¹ to A³ are eachindependently CR, or A¹ and A³ are both N and A² is CR, or one of A¹ toA³ is N and the others are independently CR.
 6. The compositionaccording to claim 4 wherein Y¹ is C, A¹ to A³ are each independentlyCR, and R⁵ is represented by the group “P” and R⁷ is represented by thegroup “Q” as follows:

wherein R¹⁹ to R²⁸ are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R¹⁹ to R²⁸are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents.
 7. The composition according to claim 3wherein the activator for the chain growth catalyst system is selectedfrom organoaluminum compounds or hydrocarbylboron compounds.